Diazotype light-sensitive material for intermediate original

ABSTRACT

There is provided a diazotype light-sensitive material for intermediate original (or substitute original), the lightsensitive material being able to give a dye-image which is easy to see and has low transmission of ultraviolet rays. Said material contains derivative of 1-hydroxynaphthalene-3,8disulfonic acid as one coupling component together with diazonium compound in the light-sensitive layer.

ilniied Siaies Paiem Shiraishi et a1.

[ Feb. 29, 1972 [54] DIAZGTYPIE LIGHT-SENSITIVE MATERIAL FORINTERMEDIATE ORIGINAL [72] Inventors: Syuhei Shiraishi, Fujisawa-shi;Tadashi Saito, Yokohama-shi, both of Japan [30] Foreign ApplicationPriority Data Jan. 9, 1969 Japan ..44/1786 [52] US. Cl ..96/91, 96/49[51] Int. Cl ..G03c 1/58 [58] Field of Search ..96/9l,49,75

[56] References Cited UNITED STATES PATENTS 1,857,920 5/1932 Lantz..96/91 2,970,909 2/1961 Slimowicz ..96/91 3,1 13,025 12/1963 Bialczak..96/91 3,248,220 4/1966 Van Rhijn.. 96/49 X 3,406,071 10/1968 Sus et..96/91 3,410,688 11/1968 Welch ..96/49 X 3,473,930 10/1969 Werner etal. ..96/49 X 2,537,098 l/1951 Sliikin et a1 ..96/91 FOREIGN PATENTS ORAPPLICATIONS 937,510 9/1963 Great Britain .,96/9l PrimaryExaminer-Charles L. Bowers, Jr. Attorney-Burgess, Ryan & Hicks [57]ABSTRACT There is provided a diazotype light-sensitive material forintermediate original (or substitute original), the light-sensitivematerial being able to give a dye-image which is easy to see and has lowtransmission of ultraviolet rays. Said material contains derivative of1-hydroxynaphthalene-3,8-disulfonic acid as one coupling componenttogether with diazonium compound in the light-sensitive layer.

4 Claims, N0 Drawings DIAZOTYPE LKGHT-SENSHTHVE MATERIAL FORHNTERMEDTATE ORIGINAL BACKGROUND OF THE INVENTION 1. Fieldof theInvention The present invention relates to a diazotype light-sensitivematerial for intermediate original.

2. Description of the Prior Art The intermediate original of thisinvention signifies an original which was produced by copying from thefirst original carrying a desired image and will be used as a substitutefor the first original. Consequently, it is to be desired that the dyeimage of the intermediate original inhibits the transmission of theultraviolet rays as much as possible. in addition, it is necessary thatthe dye-image of the intermediate original should be easy to see, sincethere are frequent occasions when something is written in it. It isunderstood that as a yellow dyestuff is an effective ultravioletabsorber, the intermediate original carrying a yellow dye-image may givecopies having a dye-image of high density. However, the yellow dye-imageis hard to see. So in order to minimize the transmission of theultraviolet rays and to get the dye-image easy to see, the browndyestuff has been added to the yellow dyestuff to produce a sepiadye-image in the prior art. This sepia dye-image, however, increases tosome extent the transmission of the ultraviolet rays because ofcoexistence of the brown dyestuff in the dye-image. As the matter offact, a black dye-image is best visible, but in order to produce it, theother dye-stuffs should be added and coexisted with the sepia dyestuff,resulting in further increase of the transmission of the ultravioletrays. The dye-image thus produced is not advisable for the dye-image ofthe intermediate original.

Diazotype light-sensitive materials for intermediate original aredisclosed in Japanese Patent Publication No. 5672/1966 and US. Pat. No,3,1 13,025.

The aforesaid No. 5672/1966 discloses that derivatives oflhydroxynaphthalene-4-alkyl-8-sulfonic acid having the following generalformula are used as a coupling component:

Said derivatives give a deep blue dye-image when coupled with diazoniumcompounds. However, as they have higher coupling activity than that ofm,m-dihydroxydiphenol or mhydroxyphenylurea which are used as couplingcomponents producing a yellow dye-image, a black dye-image cannot beobtained even when two types (blue and yellow) of the couplingcomponents are simultaneously used.

On the other hand, U.S. Pat. No. 3,113,025 discloses the compounds ofNaphthol AS type having the following general formula as couplingcomponents producing a blue dye-image:

When this compound is used together with m,m'-dihydroxydiphenol, it mayproduce a black dye-image. However, as this compound absorbs highly theultraviolet rays by itself, the transmission of the ultraviolet rays inthe nonimage area of the light-sensitive material is reduced, andconsequently copying time must be prolonged when said compound is usedas a coupling component of the light-sensitive material for intermediateoriginal.

lt is, therefore, an objectof the present invention to provide adiazotype light-sensitive material for intermediate original which givesa black dye-image having the low transmission of the ultraviolet rays.

SUMMARY OF THE INVENTION wherein X is hydrogen or an alkali metal, R ishydrogen, an alkyl group of from 1 to 4 carbon atoms, an aralkyl group,a cycloalkyl group, a hydroxylated alkyl group,

(n being an integer of from 2 to 8, R, and R being an alkyl group offrom one to four carbon atoms or a hydroxylated lower alkyl group)or(CH' ),,R- (n being an integer of from 2 to 8, R being The diazotypelight-sensitive material for intermediate original prepared by usingsaid coupling component of this invention can give an intermediateoriginal having a dye-image which is very visible and has the lowtransmission of the ultraviolet rays.

Moreover, we have found that the above-mentioned compounds, in whichsulfonic acid group has been introduced in the 4-position in lieu of3-position, have disadvantages that they give a dark blue dyestuff whencoupled with diazonium compounds, but the density of the dye-imageobtained from them is lower than that of a dye-image obtained from theabove-mentioned compounds of this invention and the color tone of thedye-image is easy to change after development in ammonia vapor.

Derivatives of monohydric phenol, which may be used together with theaforementioned coupling components and may produce a yellow azo dyestuffby coupling with dizzonium compound, are as follows:

2-(N N'-diethylaminomethyi)-3,o-dimethylphenol, m-

acetamino-phenol, m-hydroxyethylphenol, a-hydroxyphenylurea,m-hydroxyphenylurea, 3,3-dihydroxycarbanilide,m,m-ethylene-dioxydiphenol, m,m'- trimethylenedioxydiplrenol,m,mtetra-methylenedioxydiphenol, 6,6 '-dimethyl-3,3-trimethylenedioxydiphenol.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention isfurther illustrated by the following nonlimitative examples.

EXAMPLE 1 A light-sensitive solution was prepared from the followingingredients:

methyl cellosolvc l00.0 cc. cellulose acetate butyrate 2.0 g.sull'osalicylic acid 1.5 g. zinc chloride 0.2 g. m-hydroxyphenylurea 1.5g. 3-sulfonic acid (sodium salt)-l-hydroxynaphthalenc -8-sulfonic acidamide 0.45 g. p-morpholinobenzene diazoninm-BF 1.3 g.

A light-sensitive material for intermediate original was obtained byapplying said light-sensitive solution to a surface of a substrate madeof cellulose triacetate and then drying off.

This light-sensitive material gave an intermediate original having adeep greenish black dye-image by closely overlaying it on the originalcarrying a desired image, and exposing to the ultraviolet light and thendeveloping in ammonia vapor.

On the contrary, a light-sensitive material was obtained by the sameprocedure except that 0.4 g. of 3,3-dihydroxy-2- naphthoanilide(described in U.S. Pat. No. 3,1 13,025) was employed as a substitute for0.45 g. of said 3-sulfonic acid (sodium salt) -l-hydroxynapthalene-8-sulfonic acid amide. This light-sensitive material gave a reddishhalf-tone dyeimage and a slow copying speed by about 30 percent incomparison with the above-mentioned material.

EXAMPLE 2.

A light-sensitive material for intermediate original was obtained byrepeating the procedure of Example 1 except that 2.0 g.m,m-ethylenedioxydiphenol was employed as a substitute form-hydroxyphenylurea. This light-sensitive material possessed the sameproperties as that of Example 1.

EXAMPLE 3 A light-sensitive material for intermediate original wasobtained by repeating the procedure of Example l except that 0.55 g. of3-sulfonic acid (sodium salt)-l-hydroxynaphthalene-S-sulfonic acidbutyramide was employed as a substitute for 0.45 g. 3-sulfonic acid(sodium salt)-l-hydroxynaphthalene-B-sulfonic acid amide. Thislight-sensitive material possessed the same properties as that ofExample 1.

EXAMPLE 4 A light-sensitive solution was prepared from the followingingredients:

A light-sensitive material for intermediate original was obtained byrepeating the procedure of Example 1 except that said sensitive solutionwas employed. This light-sensitive material gave an intermediateoriginal having a blaclr dyeimage by treating it in the same manner asthat of Example I.

EXAMPLE 5 A light-sensitive solution was prepared from the followingingredients:

A precoat solution was prepared from the following ingredients:

copolymer of vinyl acetate and crotonic acid I 10.0 g. urea-formaldehyderesin l0.0 g. fine grain silica 5.0 g.

I000 cc.

methyl cellosolve A light-sensitive material for intermediate originalwas obtained by applying said light-sensitive solution to a substratemade of polyester, precoated with said precoat solution, and drying off.This light-sensitive material gave an intermediate original having ablack dye-image by treating it in the same manner as that of Example 1.The intermediate original thus obtained gave a nice copy by using it asan original.

We claim:

1. A diazotype light-sensitive material comprising a support having alight-sensitive layer thereon said light sensitive layer comprising adiazonium compound and a mono-hydric phenol as one coupling componentand as a second coupling component, a derivative ofl-hydroxynaphthtalene-3,8-disulfonic acid having the following formula:

XOaS- n being an integer of from 2 to 4 and R, and R each being an alkylgroup of from one to four carbon atoms, and an acidic stabilizer.

2. A light-sensitive material according to claim 1 wherein thederivative of l-hydroxynaphthalene-3,8-disulfonic acid is the sodiumsalt of 3-sulfonic acid-l-hydroxynaphthalene-8- sulfonic acid amide.

3. A light-sensitive material according to claim 1 wherein thederivative of l-hydroxynaphthalene-3,8-disulfonic acid is 3-..ulfonicacid- 1 -hyd roxynaphthalene-8-B-diethylam inoethylsulfonic acid amide.

4. A light-sensitive material according to claim 1 wherein thederivative of 1-hydroxynaphthalene-3,8-disulfonic acid is 3-sulfonicacid- 1 -hydroxynaphthalene-8 -sulfonic acid methylamide.

2. A light-sensitive material according to claim 1 wherein thederivative of 1-hydroxynaphthalene-3,8-disulfonic acid is the sodiumsalt of 3-sulfonic acid-1-hydroxynaphthalene-8-sulfonic acid amide.
 3. Alight-sensitive material according to claim 1 wherein the derivative of1-hydroxynaphthalene-3,8-disulfonic acid is 3-sulfonicacid-1-hydroxynaphthalene-8- Beta -diethylamino-ethylsulfonic acidamide.
 4. A light-sensitive material according to claim 1 wherein thederivative of 1-hydroxynaphthalene-3,8-disulfonic acid is 3-sulfonicacid-1-hydroxynaphthalene-8-sulfonic acid methylamide.